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Gas-phase NbMg n ( n = 2-12) clusters were fully searched by CALYPSO software, and then the low-energy isomers were further optimized and calculated under DFT. It is shown that the three lowest energy isomers of NbMg n ( n = 3-12) at each size are grown from two seed structures, i.e., tetrahedral and pentahedral structures, and the transition size occurs at the NbMg 8 cluster. Interestingly, the relative stability calculations of the NbMg 8 cluster ground-state isomer stand out under the examination of several parameters' calculations. The charge-transfer properties of the clusters of the ground-state isomers of various sizes had been comprehensively investigated. In order to be able to provide data guidance for future experimental probing of these ground-state clusters, this work also predicted infrared and Raman spectra at the same level of theoretical calculations. The results show that the multipeak nature of the IR and Raman spectra predicts that it is difficult to distinguish them directly. Finally, the optical properties of these clusters were investigated by calculating the static linear, second-order nonlinear, and third-order nonlinear coefficients. Importantly and interestingly, the NbMg 8 cluster was shown to have superior nonlinear optical characteristics to all other clusters; thus, it is a powerful candidate for a potentially ultrasensitive nonlinear optical response device for some special purpose., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Re-examining the relationship between neuropeptide systems and neural circuits will help us to understand more intensively the critical role of neuropeptides in brain function as the neural circuits responsible for specific brain functions are gradually revealed. Gastrin-releasing peptide receptors (GRPRs) are Gαq-coupling neuropeptide receptors and widely distributed in the brain, including hippocampus, amygdala, hypothalamus, nucleus tractus solitarius (NTS), suprachiasmatic nucleus (SCN), paraventricular nucleus of the hypothalamus (PVN), preoptic area of the hypothalamus (POA), preBötzinger complex (preBötC), etc., implying the GRP/GRPR system is involved in modulating multiple brain functions. In this review, we focus on the functionality of GRPR neurons and the regulatory role of the GRP/GRPR system in memory and cognition, fear, depression and anxiety, circadian rhythms, contagious itch, gastric acid secretion, food intake, body temperature, and sighing behavior. It can be found that GRPR is usually centered on a certain brain nucleus or anatomical structure and modulates richer or more specific behaviors by connecting with additional different nuclei. In order to explain the regulatory mechanism of the GRP/GRPR system, more precise intervention methods are needed.

Solvated electrons (e s - ) are among nature's most powerful reactants, with over 2600 reactions investigated in bulk water. These electrons can also be created at and near the surface of water by exposing an aqueous microjet in vacuum to gas-phase sodium atoms, which ionize into e s - and Na + within the top few layers. When a reactive surfactant is added to the jet, the surfactant and e s - become coreactants localized in the interfacial region. We report the reaction of e s - with the surfactant benzyltrimethylammonium in a 6.7 M LiBr/water microjet at 235 K and pH = 2. The reaction intermediates trimethylamine (TMA) and benzyl radical are identified by mass spectrometry after they evaporate from solution into the gas phase. Their detection demonstrates that TMA can escape before it is protonated and benzyl before it combines with itself or a H atom. Diffusion-reaction calculations indicate that e s - reacts on average within 20 Å of the surface and perhaps within the surfactant monolayer itself, while unprotonated TMA evaporates from the top 40 Å. The escape depth exceeds 1300 Å for the more slowly reacting benzyl radical. These proof-of-principle experiments establish an approach for exploring the near-interfacial analogues of aqueous bulk-phase radical chemistry through the evaporation of reaction intermediates into the gas phase.

Exploring potent adjuvants and new vaccine strategies is crucial for the development of protein vaccines. In this work, we synthesized a new TLR4 agonist, structurally simplified lipid A analogue GAP112, as a potent built-in adjuvant to improve the immunogenicity of SARS-CoV-2 spike RBD protein. The new TLR4 agonist GAP112 was site-selectively conjugated on the N-terminus of RBD to construct an adjuvant-protein conjugate vaccine in a liposomal formulation. It is the first time that a TLR4 agonist is site-specifically and quantitatively conjugated to a protein antigen. Compared with an unconjugated mixture of GAP112/RBD, a two-dose immunization of the GAP112-RBD conjugate vaccine strongly activated innate immune cells, elicited a 223-fold increase in RBD-specific antibodies, and markedly enhanced T-cell responses. Antibodies induced by GAP112-RBD also effectively cross-neutralized SARS-CoV-2 variants (Delta/B.1.617.2 and Omicron/B.1.1.529). This conjugate strategy provides an effective method to greatly enhance the immunogenicity of antigen in protein vaccines against SARS-CoV-2 and other diseases.

Liquid water is all around us: at the beach, in a cloud, from a faucet, inside a spray tower, covering our lungs. It is fascinating to imagine what happens to a reactive gas molecule as it approaches the surface of water in these examples. Some incoming molecules may first be deflected away after colliding with an evaporating water molecule. Those that do strike surface H 2 O or other surface species may bounce directly off or become momentarily trapped through hydrogen bonding or other attractive forces. The adsorbed gas molecule can then desorb immediately or instead dissolve, passing through the interfacial region and into the bulk, perhaps diffusing back to the surface and evaporating before reacting. Alternatively, it may react with solute or water molecules in the interfacial or bulk regions, and a reaction intermediate or the final product may then desorb into the gas phase. Building a "blow by blow" picture of these pathways is challenging for vacuum-based techniques because of the high vapor pressure of water. In particular, collisions within the thick vapor cloud created by evaporating molecules just above the surface scramble the trajectories and internal states of the gaseous target molecules, hindering construction of gas-liquid reaction mechanisms at the atomic scale that we strive to map out.The introduction of the microjet in 1988 by Faubel, Schlemmer, and Toennies opened up entirely new possibilities. Their inspired solution seems so simple: narrow the end of a glass tube to a diameter smaller than the mean free path of the vapor molecules and then push the liquid through the tube at speeds of a car on a highway. The narrow liquid stream creates a sparse vapor cloud, with water molecules spaced far enough apart that they and the reactant gases interact, at most, weakly. Experimentalists, however, confront a host of challenges: nozzle clogging, unstable jetting, searching for vacuum-compatible solutions, measuring low signal levels, and teasing out artifacts because the slender jet is the smallest surface in the vacuum chamber. In this Account, we describe lessons that we are learning as we explore gases (DCl, (HCOOH) 2 , N 2 O 5 ) reacting with water molecules and solute ions in the near-interfacial region of these fast-flowing aqueous microjets.

Dissociative electron attachments via the lowest shape resonant state 2 Π u of CO 2 - , e - + CO 2 → O - + CO, are investigated with our high-resolution anion velocity map imaging apparatus. The production efficiency curve of O - obtained in this work is consistent with those reported previously. The forward-backward asymmetric distribution superimposed on the isotopic background is observed in the time-sliced velocity image of O - yield, implying that the dissociation of CO 2 - ( 2 Π u ) proceeds through a combinational motion of bond stretching and bending. Thereby, the coproduct CO is proposed to be in the rovibrational states. The long-standing arguments about the dissociation dynamics of CO 2 - ( 2 Π u ) are settled.

The lateral habenula (LHb) is a tiny structure that acts as a hub, relaying signals from the limbic forebrain structures and basal ganglia to the brainstem modulatory area. Facilitated by updated knowledge and more precise manipulation of circuits, the progress in figuring out the neural circuits and functions of the LHb has increased dramatically over the past decade. Importantly, LHb is found to play an integrative role and has profound effects on a variety of behaviors associated with pain, including depression-like and anxiety-like behaviors, antireward or aversion, aggression, defensive behavior, and substance use disorder. Thus, LHb is a potential target for improving pain management and related disorders. In this review, we focused on the functions, related circuits, and neurotransmissions of the LHb in pain processing and related behaviors. A comprehensive understanding of the relationship between the LHb and pain will help to find new pain treatments.

The development of a safe and effective COVID-19 vaccine is of paramount importance to terminate the current pandemic. An adjuvant is crucial for improving the efficacy of the subunit COVID19 vaccine. α-Galactosylceramide (αGC) is a classical iNKT cell agonist which causes the rapid production of Th1- and Th2-associated cytokines; we, therefore, expect that the Th1- or Th2-skewing analogues of αGC can better enhance the immunogenicity of the receptor-binding domain in the spike protein of SARS-CoV-2 fused with the Fc region of human IgG (RBD-Fc). Herein, we developed a universal synthetic route to the Th1-biasing (α-C-GC) and Th2-biasing (OCH and C20:2) analogues. Immunization of mice demonstrated that αGC-adjuvanted RBD-Fc elicited a more potent humoral response than that observed with Alum and enabled the sparing of antigens. Remarkably, at a low dose of the RBD-Fc protein (2 μg), the Th2-biasing agonist C20:2 induced a significantly higher titer of the neutralizing antibody than that of Alum.

State coupling certainly determines the topologic features of the molecular potential energy surface (PES) and potentially diversifies chemical reaction pathways. Here we report the new PESs of BrCN - in the low-lying electronic states that are distinctly different from the previous predictions in the short Br-CN bond region but validated by the high-resolution ion velocity imaging measurements of low-energy dissociative electron attachment (DEA) to BrCN. Besides the vibrating CN - ions produced in the fast Br-CN bond stretching motions, we confirm that the ro-vibrating CN - ions with a nearly isotropic angular distribution are produced by receiving a torque in the combinational motion of Br-CN bond bending and stretching. The latter process is closely related to the potential well of BrCN - at the first excited state A 2 Π 3/2 that arises from the Π-Σ state couplings. Our findings not only suggest that the PESs of other anionic cyanogen halides are in dire need of reexamination but also show that ion velocity imaging of the DEA process is a powerful experimental method for evaluating the theoretical PESs of molecular anions.

Low-energy dissociative electron attachment to molecular acetonitrile (CH 3 CN) is investigated by recording the efficiency curves of CH 2 CN - , CHCN - , and CN - products, but the present curves are distinctly different from those in the previous reports. Now it is recommended that the reaction thresholds of e - + CH 3 CN → H 2 + CHCN - and CH 3 + CN - are respectively about 1.51 and 1.52 eV, and four shape-resonant states, one 2 Π and three 2 ∑, of CH 3 CN - are involved in the fragmentations at the low and high electron-attachment energies. By using a high-resolution anion velocity-map imaging spectrometer, we obtain the CN - momentum images at the electron attachment energies of 7.10, 7.60, and 8.10 eV and interpret them with four pathways concerning two- and three-body dissociations.

The timing of spring bud flush (TBF) is of economic importance for tea plant ( Camellia sinensis ) breeding. We employed a genome-wide association study (GWAS) to identify favorable single nucleotide polymorphism (SNP) allelic variations as well as candidate genes that control TBF of C. sinensis using specific-locus-amplified fragment sequencing (SLAF-seq) in a diversity panel comprising 151 tea plant germplasm resources. GWAS analysis revealed 26 SNPs associated with TBF in three years, and we eventually identified a final significant SNP for TBF. To identify candidate genes possibly related to TBF, we screened seven candidate genes within 100 kb regions surrounding the trait-related SNP loci. Furthermore, the favorable allelic variation, the "TT" genotype in the SNP loci, was discovered, and a derived cleaved amplified polymorphism (dCAPS) marker was designed that cosegregated with TBF, which could be used for marker-assisted selection (MAS) breeding in C. sinensis . The results obtained from this study can provide a theoretical and applied basis for the MAS of early breeding in tea plants in the future.

Adipic acid diselenoester was developed as an efficient cross-linker for covalent protein conjugation with a variety of small molecular haptens, including mono- and disaccharides, peptide, fluorescence dye, and nicotine. Compared to the counterparts of N-hydroxysuccinimide (NHS) and p-nitrophenyl (PNP) linkers, the diselenoester linker demonstrates improved balance between reactivity and stability and coupling of haptens to proteins under mild conditions with high incorporation efficiency.

An efficient N-linked glycosylation reaction between glycosylamines and p-nitrophenyl thioester peptides has been developed. The reaction conditions are mild and compatible with the C-terminal free carboxylic acid group and the unprotected N-linked sialyloligosaccharide. By means of this convergent strategy, a versatile N-glycopeptide fragment containing an N-terminal Thz and a C-terminal thioester was readily prepared, which is available for the synthesis of long glycopeptides and glycoproteins using the protocol of native chemical ligation.

Visible-light-induced specific desulfurization of cysteinyl peptides has been explored. The photocatalytic desulfurization catalyzed by Ru(bpy)3(2+) can proceed efficiently at room temperature in aqueous solution or in binary mixtures of aqueous/organic solvent and be compatible with the presence of residues of amino acids, carbohydrates, and various sulfur-containing functional groups. This approach was successfully applied to synthesize linear and cyclic peptides through the ligation-desulfurization protocol.

Two novel dysprosium(III) clusters have been prepared and structurally characterized. One has a tetranuclear core with a rare zigzag arrangement, and the other is an unprecedented octanuclear cluster with six triangular Dy(3) units sharing vertices. Both dysprosium(III) clusters possess frequency-dependent on alternating-current magnetic susceptibilities, indicating possible single-molecule magnet behavior.